This invention relates to novel, highly effective solid aluminoxane/metallocene olefin polymerization catalysts, their preparation, and their use.
Hydrocarbylaluminoxanes (also known as alumoxanes) complexed with transition metal compounds, such as metallocenes, have been found to be effective olefin polymerization catalysts. Methylaluminoxanes are especially effective catalyst components in forming homogeneous catalyst systems with various metallocenes. However, these catalyst systems have proven to be considerably less effective in productivity per unit weight of catalyst when used as supported heterogeneous catalysts, either in the form of dispersions in a liquid medium or as supported solid catalysts in gas-phase polymerizations. For example, in U.S. Pat. No. 5,126,301 issued Jun. 30, 1992 to Tsutsui et al. it is pointed out that when an olefin is polymerized or copolymerized in a dispersion or gas-phase polymerization system by utilizing carrier-supported metallocene-aluminoxane catalysts, polymerization activity is markedly reduced, that the properties inherent to the catalyst comprising the transition metal compound and the aluminoxane catalyst component are not fully exerted, and that powder properties such as bulk density of the thus prepared polymer were insufficient. The approach taken by Tsutsui et al. was to form a solid catalyst by contacting an xcex1-olefin with a mixture obtained by mixing an organoaluminum compound having a branched alkyl radical, an aluminoxane of specified aluminum content, a fine-particle carrier, and a transition metal metallocene compound.
Despite various improvements made during the course of extensive research activities by various laboratories, a need has existed for olefin polymerization catalysts having even better performance characteristics. For example, U.S. Pat. No. 5,498,581 issued Mar. 12, 1996 to Welch et al., points out that evaluation of attempts disclosed in U.S. Pat. Nos. 5,240,894; 4,871,705; and 5,106,804 to overcome the disadvantages of metallocene catalysts has revealed that there is still room for improvement, particularly when the catalyst is one which is to be used in a slurry-type polymerizations. The techniques disclosed in U.S. Pat. Nos. 5,240,894; 4,871,705; and 5,106,804 involve prepolymerization of the metallocene-aluminoxane catalyst system either in the presence or absence of a support.
The improved method of Welch et al. U.S. Pat. No. 5,498,581 for preparing a solid metallocene-containing catalyst system comprises (a) combining in a liquid an organoaluminoxane and at least one metallocene having at least one cyclopentadienyl, indenyl, tetrahydroindenyl, octahydrofluorenyl, or fluorenyl ligand having at least one olefinically unsaturated substituent to form a liquid catalyst system, (b) conducting prepolymerization of at least one olefin in the presence of said catalyst system to produce a prepolymerized solid catalyst containing no more than about 95 weight percent prepolymer, and (c) separating the resulting solid from the liquid and components dissolved in the liquid. The patent reports in Table I that by use of the Welch et al. method, catalysts having productivities as high as 9840 grams of polyethylene per gram of catalyst per hour were formed.
This invention provides solid olefin polymerization catalysts that are believed to have substantially higher productivities than any previously-known heterogeneous olefin catalyst or catalyst system devoid of an inorganic support and any other kind of preformed support. In addition, the polymerization catalysts of this invention possess a variety of beneficial morphological characteristics, such as for example an average (mean) particle size in the range of about 20 to about 60 microns, and a desirably narrow particle size distribution, e.g., a mean:median particle size ratio in the range of about 0.7:1 to about 1.5:1, and preferably in the range of about 0.8:1 to about 1.3:1. In fact it has been found possible to provide self-supported catalysts of this invention (i.e., particulate catalysts which are not formed using a preexisting support such as silica or preformed polyolefin particles) in which the mean:median particle size ratio is in the exceptionally narrow range of about 0.9:1 to about 1.1:1.
In addition to productivities of at least 12,000 grams of polyethylene per gram of catalyst in one hour under test conditions described hereinafter, this invention thus makes possible the provision of catalysts that have excellent morphology and handling characteristics, and that are capable of producing olefin homopolymers and copolymers having a combination of very desirable physical attributes and properties. In fact, the morphology of the particulate catalysts formed in the preferred manner of this invention is comparable to (on a par with) the best particulate catalysts previously made in these laboratories or received heretofore from outside sources. It is worth observing that such prior catalysts were formed using a silica support.
In accordance with another embodiment of this invention there is provided a particulate vinylolefin prepolymer-Group 4 metallocene-aluminoxane catalyst composition having (i) a productivity of at least 15,000 grams, and preferably at least 18,000 grams, of polyethylene per gram of catalyst in one hour, (ii) an average particle size in the range of about 20 to about 60 microns, and preferably in the range of about 22 to about 55 microns, and a mean:median particle size ratio in the range of about 0.7:1 to about 1.5:1, and preferably in the range of about 0.8:1 to about 1.3:1. More preferably the self-supported catalysts of this embodiment of the invention have a mean:median particle size ratio in the range of about 0.9:1 to about 1.1:1.
Preferred catalysts are those in which this productivity characteristic is at least 25,000, and particularly preferred catalysts are those in which this productivity characteristic is at least 30,000.
It has been discovered that particulate olefin polymerization catalysts having such exceptionally high productivities and desirable morphology can be prepared by prepolymerizing at least one vinylolefin, preferably a gaseous 1-alkene, with a Group 4 metallocene-aluminoxane solution, provided the proportion of vinylolefin (most preferably, ethylene) relative to the Group 4 metallocene(s) used in forming the solution is suitably controlled. Typically these reactants are proportioned so that the prepolymerized catalyst composition contains (i. e., is formed by prepolymerization of) from about 150 to about 1500, and preferably in the range of about 175 to about 1000, moles of vinylolefin per mole of metallocene. It is also important in carrying out this process to use a solution in which the atom ratio of aluminum to Group 4 metal in the solution is within a suitable range, e.g., in a range of at least about 50:1 or more usually at least about 100:1, and in either case up to about 1500:1, or more usually up to about 1000:1. Typically the atom ratio of aluminum to Group 4 metal is the range of about 150:1 to about 1500:1, and preferably in the range of about 175:1 to about 1000:1. In addition, the Group 4 metallocene ingredient used in forming these new, highly productive catalysts has in its molecular structure at least one polymerizable olefinic substituent. Of these Group 4 metallocenes, the zirconium metallocenes are most preferred, especially those containing two cyclopentadienyl moiety-containing groups in the molecule. These two groups can be unbridged, but preferably are connected to each other by a bridging group.
Another feature of these catalysts is that they are self-supporting catalysts. By this is meant that the catalyst particles do not contain, and thus are not produced in the presence of, a preformed support such as an inorganic compound (silica or etc.) or a preformed particulate polymeric support. Instead, the prepolymer is formed in the presence of the combination of at least one Group 4 metallocene and at least one aluminoxane in an initially homogeneous liquid organic solvent phase from which the catalyst particles precipitate, wherein such combination is in whatever chemical composition or makeup it assumes or acquires when the metallocene and the aluminoxane are brought together in the solvent. According to the present state of knowledge in the art, when a metallocene and an aluminoxane are brought together in an inert organic solvent they are understood to undergo chemical reaction with each other to thereby form a reaction product. Accordingly, in accordance with the present state of knowledge in the art, the prepolymer of the catalyst compositions of this invention is believed to be formed in the presence of the reaction product of at least one Group 4 metallocene and at least one aluminoxane in an initially homogeneous organic liquid solvent phase from which the catalyst particles precipitate. Some excess aluminoxane may also be present.
A further embodiment of this invention is a self-supported vinylolefin-prepolymerized Group 4 metallocene-aluminoxane particulate catalyst composition devoid of a preformed support and that has (i) a productivity of at least 12,000, more desirably at least 15,000, and still more desirably at least 18,000, grams of polyethylene per gram of catalyst if and when tested as described herein, and (ii) a particle size distribution in which 75% of the catalyst has a particle size below 70 microns and 25% of the catalyst has a particle size of 70 microns or above, in which 50% of the catalyst has a particle size below about 62 microns and 50% of the catalyst has a particle size of 62 microns or above, in which 25% of the catalyst has a particle size below 45 microns and 75% of the catalyst has a particle size of 45 microns or above, and in which no more than 5%, and preferably no more than about 2%, of the catalyst has a particle size above 400 microns. More preferably, no more than 3%, and still more preferably no more than about 1%, of the catalyst has a particle size above 300 microns. All percentages given in this paragraph are volume percentages. Preferably, the self-supported vinylolefin-prepolymerized Group 4 metallocene-aluminoxane particulate catalyst compositions devoid of a preformed support referred to in this paragraph are self-supported ethylene-prepolymerized Group 4 metallocene-aluminoxane particulate catalyst compositions devoid of a preformed support, and even more preferably, the Group 4 metal in the metallocene is zirconium. Still more preferably, there is only a single atom of zirconium in the molecule of the zirconium metallocene before it is used in the formation of these catalyst compositions.
In preferred embodiments, the above catalysts of this invention have a specific surface area of no more than about 20 square meters per gram (m2/g), and preferably less than 10 m2/g.
In other preferred embodiments, there is provided a self-supported vinylolefin-prepolymerized Group 4 metallocene-aluminoxane particulate catalyst composition devoid of a preformed support and having a particle size distribution in which 90% of the catalyst has a particle size below 80 microns and 10% of the catalyst has a particle size of 80 microns or above, in which 75% of the catalyst has a particle size below 70 microns and 25% of the catalyst has a particle size of 70 microns or above, in which 50% of the catalyst has a particle size below about 62 microns and 50% of the catalyst has a particle size of 62 microns or above, in which 25% of the catalyst has a particle size below 45 microns and 75% of the catalyst has a particle size of 45 microns or above, and in which 10% of the catalyst has a particle size below 25 microns and 90% of the catalyst has a particle size of 25 microns or above, all such percentages being by volume. In another preferred embodiment these self-supported vinylolefin-prepolymerized Group 4 metallocene-aluminoxane particulate catalyst compositions devoid of a preformed support have, in addition to such particle size distributions, an average (mean) particle size in the range of about 20 to about 60 microns. Preferably, the self-supported vinylolefin-prepolymerized Group 4 metallocene-aluminoxane particulate catalyst compositions devoid of a preformed support referred to in this paragraph are self-supported ethylene-prepolymerized Group 4 metallocene-aluminoxane particulate catalyst compositions devoid of a preformed support, and even more preferably, the Group 4 metal in the metallocene is zirconium. Still more preferably, there is only a single atom of zirconium in the molecule of the zirconium metallocene before it is used in the formation of these catalyst compositions.
The catalyst compositions described in the immediately preceding paragraph typically have a productivity of at least 12,000, more desirably at least 15,000, and still more desirably at least 18,000, grams of polyethylene per gram of catalyst if and when tested as described herein. A few instances wherein the productivity of the catalyst was below these values, e.g., 8400 or 7200 grams of polyethylene per gram of catalyst are deemed anomalous results.
To test for productivity, a fresh catalyst is tested in slurry form for productivity with ethylene in a 2-liter autoclave that has been precharged with about one liter of isobutane and that is charged with ethylene to a total pressure of 450 psig at 91.5xc2x0 C., for one hour. The amount in grams of dried polyethylene produced in under these conditions per gram of the catalyst constitutes the productivity of the catalyst.
A preferred method for producing the highly productive catalysts of this invention is a process which comprises:
a) mixing together in an organic solvent medium at least one metallocene, preferably a metallocene of a Group 4 metal, and at least one aluminoxane, preferably a methylaluminoxane to form a catalytic solution; and
b) contacting catalytic solution from a) with a controlled amount of vinylolefin monomer, preferably ethylene, under polymerization conditions such that particulate solids are formed having a specific surface area of no more than about 20 square meters per gram (m2/g).
When performed properly, the recovered and dried catalyst has a productivity of at least 18,000 grams of polyethylene per gram of catalyst in one hour.
It is interesting to compare the unsupported catalysts of this invention and the productivity thereof with the catalysts and productivity (xe2x80x9cpolymerization activityxe2x80x9d) of the catalysts reported in U.S. Pat. No. 4,923,833 issued to Kioka et al. on May 8, 1990. Unlike the present invention, Kioka et al. produce solid unsupported catalysts by (a) contacting a solution of an aluminoxane in a first solvent with a second solvent in which the aluminoxane is insoluble or sparingly soluble, to precipitate solid aluminoxane to form a suspension, and (b) contacting the resulting suspension of solid aluminoxane with a solution of a compound of a Group 4 metal, such as a metallocene thereof, in a third solvent, to form solid fine particles. Thereafter ethylene is fed to the solution to effect prepolymerization. Thus the Kioka et al. solid particles are formed first by precipitating the aluminoxane as solid particles and then causing the interaction between the metallocene and the aluminoxane. In contrast, the present invention involves interacting the metallocene and the aluminoxane in solution, and introducing a controlled amount of ethylene or other vinyl monomer to cause formation of solid particles in the liquid medium. The highest productivity shown in the Kioka et al. patent for their catalysts is in Example 6 wherein the productivity (xe2x80x9cpolymerization activityxe2x80x9d) was 27,100 g PE/mM Zr in a slurry polymerization process in which an ethylene-4-methyl-1-pentene copolymer was produced. When expressing productivity on the same basis as used by Kioka et al., the catalysts of the present invention have a xe2x80x9cpolymerization activityxe2x80x9d of at least about 600,000 g PE/mM Zr.
Other embodiments and features of the invention will become still further apparent from the ensuing description and appended claims.
Hydrocarbylaluminoxanes are formed by the partial hydrolysis of hydrocarbyl-aluminum compounds and, especially, trialkylaluminums such as trimethylaluminum.
Hydrocarbylaluminoxanes may exist in the form of linear, cyclic, caged or polymeric structures with the simplest monomeric compounds being a tetraalkylaluminoxane such as tetramethylaluminoxane of the formula (CH3)2AlOAl(CH3)2, or tetraethylaluminoxane of the formula (C2H5)2AlOAl(C2H5)2. The compounds preferred for use in olefin polymerization catalysts are oligomeric materials, sometimes referred to as polyalkyl-aluminoxanes, which usually contain about 4 to 20 of the repeating units: 
where R is C1-C10 alkyl. Especially preferred are polymethylaluminoxanes (MAOs). Although the linear and cyclic aluminoxanes are often noted as having the structures 
where m and n are integers of 4 or more, the exact configuration of the aluminoxanes remains unknown.
Methylaluminoxanes can contain some higher alkyl groups to improve their solubility. Such modified methylaluminoxanes are described, for example, in U.S. Pat. No. 5,157,008. Besides MAO, non-limiting examples of hydrocarbylaluminoxanes for use in the invention include ethylaluminoxane (EAO), isobutylalumidnoxane (IBAO), n-propylaluminoxane, n-octylaluminoxane, and the like. The hydrocarbylaluminoxanes can also contain up to about 20 mole percent (based on aluminum) of moieties derived from amines, alcohols, ethers, esters, phosphoric and carboxylic acids, thiols, alkyl disiloxanes and the like to improve their activity, solubility and/or stability.
The aluminoxanes can be prepared as known in the art by the partial hydrolysis of trialkylaluminum compounds. The trialkylaluminum compounds can be hydrolyzed by reacting them with either free water or water containing solids, which can be either hydrates or porous materials which have absorbed water. Because it is difficult to control the reaction by adding water per se, even with vigorous agitation of the mixture, the free water is usually added in the form of a solution or a dispersion in an organic solvent. Suitable hydrates include salt hydrates such as, for example, CuSO4.5H2O, Al2(SO4)3.18H2O, FeSO4.7H2O, AlCl3.6H2O, Al(NO3)3.9H2O, MgSO4.7H2O, MgCl2.6H2O,ZnSO4.7H2O, Na2SO4.10H2O, Na3PO4.12H2O, LiBr.2H2O, LiCl.1H2O, LiI.2H2O, LiI.3H2O, KF.2H2O, NaBr.2H2O and the like and alkali metal or alkaline earth metal hydroxide hydrates such as, for example, NaOH.H2O, NaOH.2H2O, Ba(OH)2. 8H2O, KOH.2H2O, CsOH.1H2O, LiOH.1H2O and the like. Mixtures of any of the above hydrates can be used. The mole ratios of free water or water in the hydrate or in porous materials such as alumina or silica to total alkyl aluminum compounds in the mixture can vary widely, such as for example from about 2:1 to 1:4, with ratios of from about 4:3 to 1:3.5 being preferred.
Such hydrocarbylaluminoxanes and processes for preparing hydrocarbylaluminoxanes are described, for example, in U.S. Pat. Nos. 4,908,463; 4,924,018; 5,003,095; 5,041,583; 5,066,631; 5,099,050; 5,157,008; 5,157,137; 5,235,081; 5,248,801, and 5,371,260, whose entire teachings are incorporated herein by reference. The methyl-aluminoxanes contain varying amounts, of from about 5 to 35 mole percent, of the aluminum value as unreacted trimethylaluminum. Preferably, the aluminum content as trimethyl aluminum is less than about 23 mole percent of the total aluminum value, and, more preferably, less than about 20 mole percent.
The Aluminoxanes can be used as supplied or they can be subjected to a heat treatment prior to being used in forming the catalyst compositions of this invention. While it may be possible to heat treat the aluminoxane while in neat form, it is preferable to heat a solution or slurry of one or more aluminoxanes, preferably methylaluminoxane, in a suitable inert anhydrous solvent such as a hydrocarbon solvent. Paraffinic and cycloparaffinic hydrocarbon solvents which can be used to form solutions or slurries of the aluminoxanes include pentane, isopentane, hexane, cyclohexane, heptane, octane, decane, dodecane, hexadecane, and the like, with those having carbon numbers of 5 to 10 being preferred. Liquid mononuclear aromatic hydrocarbons which can be used include such solvents as benzene, toluene, one or more xylenes, cumene, ethylbenzene, mesitylene, and aromatic hydrocarbon mixtures or blends such as aromatic naphthas, BTX, aromatic gasoline fractions, with those having carbon numbers of 6 to 20 being preferred. As a class, the aromatic solvents are preferred.
When utilizing previously heat-treated aluminoxanes in forming the particulate catalysts of this invention, it is desirable to use one or more aluminoxanes that have been heat treated while in a hydrocarbon solution which, before heat treatment, contains at least about 5 wt % and up to about 50 wt % or more, preferably in the range of about 10 to about 40 wt %, and more preferably in the range of about 25 to about 30 wt % of one or more hydrocarbylaluminoxanes, especially methylaluminoxane, in whatever form or composition such compounds exist while in such solution. The solvent is usually a paraffinic, cycloparaffinic and/or aromatic solvent, and most preferably is a liquid mononuclear aromatic hydrocarbon solvent (e.g., toluene or xylene). Heating the solution at a temperature of at least about 40xc2x0 C. for a suitable period of time can increase the productivity of catalyst compositions of this invention made using such heat-treated aluminoxane(s). It has been observed that by heating a visually clear solution of a freshly-produced methylaluminoxane in an aromatic solvent such as toluene at a temperature of at least about 40xc2x0 C., and preferably at least about 70xc2x0 C., for a suitable period of time the resultant solution, when chilled to a suitably low temperature such as xe2x88x9215xc2x0 C. for about 8 hours, will contain a visually perceptible amount of gel whereas the same methylaluminoxane solution which has not been heat treated does not exhibit visually perceptible gel formation when chilled in the same manner. Similarly, such heat treatment, if applied to an aged methylaluminoxane-toluene solution which already contains a visually perceptible amount of gel, tends to result in an increased amount of visually perceptible gel content after maintaining the heat treated solution at xe2x88x9215xc2x0 C. for 8 hours. At present it is not known exactly what is taking place during the heating of the aluminoxane solution, or why the resultant heat-treated aluminoxane solution can increase the activity of catalyst compositions made therefrom.
Aluminoxane heat treatment temperatures in the range of about 40 up to about 130xc2x0 C. are typical, and the preferred temperatures, especially when heat-treating methylaluminoxanes, are in the range of about 70 to about 90xc2x0 C. The duration of the time periods during which the aluminoxane is heated will vary depending chiefly upon the temperature(s) being used and the concentration of the initial aluminoxane solution, in general the higher the temperature and/or concentration, the shorter the time. Typically the time periods will fall in the range of about 0.5 to about 72 hours and with preferred temperatures and aluminoxane concentrations, time periods in the range of about 1 to about 12 hours will normally suffice. For example, with 30 wt % methylaluminoxane solutions in toluene or equivalent aromatic solvent, heating at 80xc2x0 C. for from about 2 to about 12 hours is a preferred way to operate. It will be understood that on the basis of this disclosure, departures from the foregoing ranges of temperatures, times and/or initial aluminoxane concentrations may be made whenever deemed necessary or desirable.
As used in the specification and claims, the term xe2x80x9cmetallocenexe2x80x9d includes metal derivatives which contain at least one cyclopentadienyl moiety. The metallocenes used in forming the self-supported, solid catalysts of this invention are those having at least one, and most preferably only one, polymerizable olefinic substituent such as a hydrocarbyl group having a terminal carbon-to-carbon double bond in the molecule. Such substituent(s) can be present (a) on a cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, benzoindenyl or like cyclopentadienyl-moiety-containing group of the metallocene, (b) on a bridging group linking a pair of cyclopentadienyl-moiety-containing groups together in the metallocene, (c) on the Group 4 metal atom of the metallocene, or (d) on any two or more of (a), (b), and (c). Examples of such terminal olefinically substituted metallocenes are metallocenes of the type disclosed or taught, for example, in U.S. Pat. No. 5,145,819 to Winter et. al., U.S. Pat. No. 5,169,818 to Antberg et al., U.S. Pat. No. 5,498,581 to Welch et al., and U.S. Pat. No. 5,541,350 to Murata et al., the complete disclosures of which are incorporated herein by reference.
For best results, the metallocene component used in forming the compositions of this invention contains only one atom of the Group 4 metal per molecule, i.e., for best results the metallocene used does not contain a polymeric backbone to which are attached a plurality of metallocene moieties. Also preferred are metallocenes which contain only one polymerizable olefinic substituent per molecule. A few such olefinically substituted metallocenes containing only one Group 4 metal atom per molecule include the following:
(cyclopentadienyl)(vinylcyclopentadienyl)zirconium dichloride,
bis(vinylcyclopentadienyl)zirconium dichloride,
bis(2,3-dimethyl-5-vinylcyclopentadienyl)zirconium dichloride,
(cyclopentadienyl)(vinylcyclopentadienyl)zirconium dimethyl,
bis(vinylcyclopentadienyl)zirconium dimethyl,
bis(2,3-dimethyl-5-vinylcyclopentadienyl)zirconium dimethyl,
(cyclopentadienyl)(vinylcyclopentadienyl)hafnium dichloride,
bis(vinylcyclopentadienyl)hafnium dichloride,
bis(2,3-dimethyl-5-vinylcyclopentadienyl)hafnium dichloride,
(cyclopentadienyl)(vinylcyclopentadienyl)hafnium dimethyl,
bis(vinylcyclopentadienyl)hafnium dimethyl,
bis(2,3-dimethyl-5-vinylcyclopentadienyl)hafnium dimethyl,
(divinylsilyl)bis(indenyl)zirconium dichloride (also known as divinylsilanediylbis(indenyl)-zirconium dichloride),
(divinylsilyl)bis(2-methylindenyl)zirconium dichloride,
(divinylsilyl)bis(2-ethylindenyl)zirconium dichloride,
(diallylsilyl)bis(indenyl)zirconium dichloride,
(diallylsilyl)bis(2-methylindenyl)zirconium dichloride,
(diallylsilyl)bis(2-ethylindenyl)zirconium dichloride,
(diallylsilyl)bis(indenyl)zirconium dichloride,
(methylvinylsilyl)bis(indenyl)zirconium dichloride,
(methylallylsilyl)bis(indenyl)zirconium dichloride,
(divinylsilyl)bis(2-methylindenyl)zirconium dimethyl,
(divinylsilyl)bis(2-ethylindenyl)zirconium dimethyl,
(diallylsilyl)bis(2-methylindenyl)zirconium dimethyl,
(diallylsilyl)bis(2-ethylindenyl)zirconium dimethyl,
(divinylsilyl)bis(2-methylindenyl)zirconium(methyl)(phenyl),
(methylvinylsilyl)bis(indenyl)zirconium dimethyl,
(methylallylsilyl)bis(indenyl)zirconium dimethyl,
(cyclopentadienyl)(vinylcyclopentadienyl)hafnium dichloride,
bis(vinylcyclopentadienyl)hafnium dichloride,
bis(2,3-dimethyl-5-vinylcyclopentadienyl)hafnium dichloride,
(cyclopentadienyl)(vinylcyclopentadienyl)hafnium dimethyl,
bis(vinylcyclopentadienyl)hafnium dimethyl,
bis(2,3-dimethyl-5-vinylcyclopentadienyl)hafnium dimethyl,
(cyclopentadienyl)(vinylcyclopentadienyl)hafnium dichloride,
bis(vinylcyclopentadienyl)hafnium dichloride,
bis(2,3-dimethyl-5-vinylcyclopentadienyl)hafnium dichloride,
(cyclopentadienyl)(vinylcyclopentadienyl)hafnium dimethyl,
bis(vinylcyclopentadienyl)hafnium dimethyl,
bis(2,3-dimethyl-5-vinylcyclopentadienyl)hafnium dimethyl,
(divinylsilyl)bis(indenyl)hafnium dichloride (also known as divinylsilanediylbis(indenyl) hafnium dichloride),
(divinylsilyl)bis(2-methylindenyl)hafnium dichloride,
(divinylsilyl)bis(2-ethylindenyl)hafnium dichloride,
(diallylsilyl)bis(indenyl)hafnium dichloride,
(diallylsilyl)bis(2-methylindenyl)hafnium dichloride,
(diallylsilyl)bis(2-ethylindenyl)hafnium dichloride,
(diallylsilyl)bis(indenyl)hafnium dichloride,
(methylvinylsilyl)bis(indenyl)hafnium dichloride,
(methylallylsilyl)bis(indenyl)hafnium dichloride,
(divinylsilyl)bis(2-methylindenyl)hafnium dimethyl,
(divinylsilyl)bis(2-ethylindenyl)hafnium dimethyl,
(diallylsilyl)bis(2-methylindenyl)hafnium dimethyl,
(diallylsilyl)bis(2-ethylindenyl)hafnium dimethyl,
(divinylsilyl)bis(2-methylindenyl)hafnium(methyl)(phenyl),
(methylvinylsilyl)bis(indenyl)hafnium dimethyl,
(methylallylsilyl)bis(indenyl)hafnium dimethyl,
(diallylamino)(methyl)silylbis(cyclopentadienyl)titanium dichloride,
(diallylamino)(phenyl)silylbis(cyclopentadienyl)titanium dichloride,
(diallylamino)(methyl)silylbis(cyclopentadienyl)titanium dimethyl,
(diallylamino)(phenyl)silylbis(cyclopentadienyl)titanium dimethyl,
bis[(diallylamino)]silylbis(cyclopentadienyl)titanium dichloride,
bis[(diallylamino)]silylbis(cyclopentadienyl)titanium dimethyl,
bis[(diallylamino)]silylbis(methylcyclopentadienyl)titanium dichloride,
bis[(diallylamino)]silylbis(methylcyclopentadienyl)titanium dimethyl,
bis[(diallylamino)]silylbis(indenyl)titanium dichloride,
bis[(diallylamino)]silylbis(indenyl)titanium dimethyl,
bis[(diallylamino)]silylbis(2-methylindenyl)titanium dichloride,
bis[(diallylamino)]silylbis(2-methylindenyl)titanium dimethyl,
bis[(diallylamino)]silylbis(pentamethylcyclopentadienyl)titanium dichloride,
bis[(diallylamino)]silylbis(pentamethylcyclopentadienyl)titanium dimethyl,
(diallylamino)(methyl)silylbis(cyclopentadienyl)zirconium dichloride,
(diallylamino)(phenyl)silylbis(cyclopentadienyl)zirconium dichloride,
(diallylamino)(methyl)silylbis(cyclopentadienyl)zirconium dimethyl,
(diallylamino)(phenyl)silylbis(cyclopentadienyl)zirconium dimethyl,
bis[(diallylamino)]silylbis(cyclopentadienyl)zirconium dichloride,
bis[(diallylamino)]silylbis(cyclopentadienyl)zirconium dimethyl,
bis[(diallylamino)]silylbis(methylcyclopentadienyl)zirconium dichloride,
bis[(diallylamino)]silylbis(methylcyclopentadienyl)zirconium dimethyl,
bis[(diallylamino)]silylbis(indenyl)zirconium dichloride,
bis[(diallylamino)]silylbis(indenyl)zirconium dimethyl,
bis[(diallylamino)]silylbis(2-methylindenyl)zirconium dichloride,
bis[(diallylamino)]silylbis(2-methylindenyl)zirconium dimethyl,
bis[(diallylamino)]silylbis(pentamethylcyclopentadienyl)zirconium dichloride,
bis[(diallylamino)]silylbis(pentamethylcyclopentadienyl)zirconium dimethyl,
(diallylamino)(methyl)silylbis(cyclopentadienyl)hafnium dichloride,
(diallylamino)(phenyl)silylbis(cyclopentadienyl)hafnium dichloride,
(diallylamino)(methyl)silylbis(cyclopentadienyl)hafnium dimethyl,
(diallylamino)(phenyl)silylbis(cyclopentadienyl)hafnium dimethyl,
bis[(diallylamino)]silylbis(cyclopentadienyl)hafnium dichloride,
bis[(diallylamino)]silylbis(cyclopentadienyl)hafnium dimethyl,
bis[(diallylamino)]silylbis(methylcyclopentadienyl)hafnium dichloride,
bis[(diallylamino)]silylbis(methylcyclopentadienyl)hafnium dimethyl,
bis[(diallylamino)]silylbis(indenyl)hafnium dichloride,
bis[(diallylamino)]silylbis(indenyl)hafnium dimethyl,
bis[(diallylamino)]silylbis(2-methylindenyl)hafnium dichloride,
bis[(diallylamino)]silylbis(2-methylindenyl)hafnium dimethyl,
bis[(diallylamino)]silylbis(pentamethylcyclopentadienyl)hafnium dichloride,
bis[(diallylamino)]silylbis(pentamethylcyclopentadienyl)hafnium dimethyl,
bis(cyclopentadienyl)zirconium diallyl,
bis(methylcyclopentadienyl)zirconium diallyl,
bis(2,3,5-trimethylcyclopentadienyl)zirconium diallyl,
(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium diallyl,
bis(methylindenyl)zirconium diallyl,
(indenyl)(2-methylindenyl)zirconium diallyl,
bis(cyclopentadienyl)hafnium diallyl,
bis(methylcyclopentadienyl)hafnium diallyl,
bis(2,3,5-trimethylcyclopentadienyl)hafnium diallyl,
(cyclopentadienyl)(pentamethylcyclopentadienyl)hafnium diallyl,
bis(methylindenyl)hafnium diallyl,
(indenyl)(2-methylindenyl)hafnium diallyl.
Preferred metallocenes include such compounds as the following:
5-(cyclopentadienyl)-5-(9-fluorenyl) 1-hexene zirconium dichloride,
bis(9-fluorenyl)(methyl)(vinyl)silane zirconium dichloride,
bis(9-fluorenyl)(methyl)(prop-2-enyl)silane zirconium dichloride,
bis(9-fluorenyl)(methyl)(but-3-enyl)silane zirconium dichloride,
bis(9-fluorenyl)(methyl)(hex-5-enyl)silane zirconium dichloride,
bis(9-fluorenyl)(methyl)(oct-7-enyl)silane zirconium dichloride,
(cyclopentadienyl)(1-allylindenyl) zirconium dichloride,
bis(1-allylindenyl)zirconium dichloride,
(9-(prop-2-enyl)fluorenyl)(cyclopentadienyl)zirconium dichloride,
(9-(prop-2-enyl)fluorenyl)(pentamethylcyclopentadienyl)zirconium dichloride,
bis(9-(prop-2-enyl)fluorenyl) zirconium dichloride,
(9-(cyclopent-2-enyl)fluorenyl)(cyclopentadienyl) zirconium dichloride,
bis(9-(cyclopent-2-enyl)(fluorenyl)zirconium dichloride,
5-(2-methylcyclopentadienyl)-5(9-fluorenyl)-1-hexene zirconium dichloride,
1-(9-fluorenyl)-1-(cyclopentadienyl)-1-(but-3-enyl)-1-(methyl)methane zirconium dichloride,
5-(fluorenyl)-5-(cyclopentadienyl)-1-hexene hafnium dichloride,
(9-fluorenyl)(1-allylindenyl)dimethylsilane zirconium dichloride,
1-(2,7-di(alpha-methylvinyl)(9-fluorenyl)-1-(cyclopentadienyl)-1,1-dimethylmethane zirconium dichloride,
1-(2,7-di(cyclohex-1-enyl)(9-fluorenyl))-1-(cyclopentadienyl)-1,1-methane zirconium di-chloride,
5-(cyclopentadienyl)-5-(9-fluorenyl)-1-hexene titanium dichloride,
5-(methylcyclopentadienyl)-5-(9-fluorenyl) 1-hexene titanium dichloride,
bis(9-fluorenyl)(methyl)(vinyl)silane titanium dichloride,
bis(9-fluorenyl)(methyl)(prop-2-enyl)silane titanium dichloride,
bis(9-fluorenyl)(methyl)(but-3-enyl)silane titanium dichloride,
bis(9-fluorenyl)(methyl)(hex-5-enyl)silane titanium dichloride,
bis(9-fluorenyl)(methyl)(oct-7-enyl)silane titanium dichloride,
(cyclopentadienyl)(1-allylindenyl) titanium dichloride,
bis(1-allylindenyl)titanium dichloride,
(9-(prop-2-enyl)fluorenyl)(cyclopentadienyl)hafnium dichloride,
(9-(prop-2-enyl)fluorenyl)(pentamethylcyclopentadienyl)hafnium dichloride,
bis(9-(prop-2-enyl)fluorenyl) hafnium dichloride,
(9-(cyclopent-2-enyl)fluorenyl)(cyclopentadienyl) hafnium dichloride,
bis(9-(cyclopent-2-enyl)(fluorenyl)hafnium dichloride,
5-(2-methylcyclopentadienyl)-5(9-fluorenyl)-1-hexene hafnium dichloride,
5-(fluorenyl)-5-(cyclopentadienyl)-1-octene hafnium dichloride,
(9-fluorenyl)(1-allylindenyl)dimethylsilane hafnium dichloride.
It will be noted that the metallocene ingredients are metallocenes of a Group 4 metal, namely, titanium, zirconium or hafnium preferably having two cyclopentadienyl moiety-containing groups which can be separate moieties or they can be joined or connected together by means of a bridge such as, for example, a divalent hydrocarbyl bridge, a silicon-containing divalent bridge, or a germanium-containing divalent bridge, and in any case the metallocene contains polymerizable olefinic substitution in the molecule. Of the Group 4 metals, metallocenes of zirconium are preferred. Particularly preferred metallocenes are those which contain in the molecule only one atom of zirconium, only one polymerizable olefinic substituent, and two cyclopentadienyl moiety-containing groups. In addition these particularly preferred metallocenes do not contain a polymeric backbone to which are attached a plurality of metallocene moietiesxe2x80x94i.e., they are not formed by grafting a metallocene onto a preexisting polymeric backbone. In these particularly preferred metallocenes the two cyclopentadienyl moieties can be unbridged, but more preferably are connected or joined together by a bridging group.
As noted above, two or more of the above metallocenes can be used in forming the catalysts of this invention. Likewise, one or more of the above metallocenes containing at least one polymerizable olefinic substituent can be used in combination with one or more Group 4 metallocenes which are devoid of polymerizable olefinic substitution. These latter metallocenes are, in general, the same kind of compounds as the metallocenes described above except that they do not contain any polymerizable olefinic substitution. Thus for example these metallocenes that are devoid of polymerizable olefinic substitution contain in the molecule (A) at least one, and preferably only one, atom of a Group 4 metal and (B) at least one cyclopentadienyl moiety-containing group, and preferably two cyclopentadienyl moiety-containing groups. When two cyclopentadienyl moiety-containing groups are present they can be unbridged or they can be connected together by a bridging group of the type such as described above.
Suitable transition metal compounds which may be used together with the metallocene include the well known Ziegler-Natta catalyst compounds of Group 4-6 metals. Non-limiting illustrative examples of such transition metals include TiC 4, TiBr4, Ti(OC2H5)3Cl, Ti(OC2H5)Cl3, Ti(OC4H9)3Cl, Ti(OC3H7)2Cl2, Ti(OC3H7)2Br2, VCl4, VOCl3, VO(OC2H5)3, ZrCl4, ZrCl3(OC2H5), Zr(OC2H5)4, ZrCl(OC4H9)3, and the like.
In general, any polymerizable olefinic hydrocarbon or combination of polymerizable olefinic hydrocarbons can be used in forming the catalyst compositions of this invention. Typically, they are one or more alpha-olefins having up to about 18 carbon atoms, although alpha-olefin monomers having even higher carbon atom contents may be used. A few examples include styrene, 1-pentene, 4-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene,1-octadecene, and vinylcyclohexane. Preferred are vinyl olefins having up to about 8 carbon atoms, and more preferred are the vinyl olefinic hydrocarbons (1-alkenes) having from 2 to 4 carbon atoms, namely ethylene, propylene and 1-butene or combinations of any two or all three of these. Combinations of ethylene or propylene with another vinyl olefinic hydrocarbon such as 1-pentene, 1-hexene or 1-octene are also suitable. Ethylene itself is the most preferred olefin for use in forming the self-supported catalysts of this invention.
In the practice of this invention the particulate catalyst compositions of this invention are not made in the presence of a preformed organic or inorganic solid support. Thus the prepolymerization solution is free of any such support, and the particulate vinylolefin prepolymer-Group 4 metallocene-aluminoxane catalyst compositions of this invention are devoid or free of preformed particulate solids except possibly for trace amounts (e.g.,  less than 0.5 wt %) of solid impurities that may be present as adventitious impurities in the materials or reaction equipment used in preparing the catalyst particles.
The hydrocarbon solution in which the prepolymerization is to be performed should contain the aluminoxane and metallocene ingredients (or the reaction product(s) formed in situ therefrom) in proportions such that the atom ratio of aluminum to Group 4 metal in the solution is in the range of about 150:1 to about 1500: 1, and preferably in the range of about 175:1 to about 1000:1.
As noted above, the proportion of vinylolefin (most preferably, ethylene) to metallocene reacted in the prepolymerization step is in the range of about 150 to about 1500, and preferably in the range of about 175 to about 1000, moles per mole of Group 4 metallocene used in forming the solution in which the prepolymerization is to be conducted. Surprisingly, if the mole ratio of vinylolefin to Group 4 metallocene used in this process step is significantly above the maximum mole ratio utilized pursuant to this invention, the morphology of the catalyst particles becomes very poor. Thus pursuant to this invention, less rather than more vinylolefin is used in forming the prepolymerized catalyst particles. When using a polymerizable gaseous vinylolefin such as ethylene in the prepolymerization reaction, the amount of the gaseous vinylolefin which is reacted in the prepolymerization is typically measured by use of a suitably-calibrated mass flow meter.
The prepolymerization can be conducted under relatively mild conditions. Typically, this would involve using low pressures of the olefin and relatively low temperatures designed to prevent site decomposition resulting from high concentrations of localized heat. The prepolymerization typically occurs at temperatures in the range of about xe2x88x9215xc2x0 C. to about +110xc2x0 C., more preferably in the range of about +100 to about +30xc2x0 C. The amount of prepolymer can be varied but typically would be in the range of from about 1 to about 95 wt % of the resulting prepolymerized solid catalyst system more preferably about 5 to 80 wt %. It is generally desirable to carry out the prepolymerization to at least a point where substantially all of the metallocene is in the solid rather than in the liquid since that maximizes the use of the metallocene.
In a preferred embodiment, the metallocene used has only one Group 4 metal atom per molecule, and the prepolymerization reaction is conducted at a temperature of about 15xc2x0 C. or below. Use of such low temperatures with hydrocarbon solutions containing desirably high concentrations of the aluminoxane and the metallocene and/or a preformed mixture or reaction product formed therefrom (e.g., about 15 wt % or more of the aluminoxane and about 1.5 wt % or more of the metallocene in the hydrocarbon solvent medium) the prepolymerization reaction tends to produce self-supported products having higher productivities as compared to use under the same conditions of higher temperatures, such as room temperature or above.
When carrying out the processes of this invention, products with highest productivities tend to be formed by suitable coordination between reaction temperature and concentration of the aluminoxane and the metallocene in the prepolymerization reaction solvent. For example, when it is desired to conduct the prepolymerization at about 25xc2x0 C., the reaction solution before prepolymerization should be composed of about 96 to about 99 wt %, preferably about 96.5 to about 98 wt %, and more preferably about 96.8 to about 97.5 wt %, of the hydrocarbon solvent with the balance to 100% being the MAO and metallocene (proportioned as described above), especially when the aluminoxane used is methylaluminoxane (MAO) and the metallocene used is one of the above-listed preferred metallocenes. Operation at 25xc2x0 C. with a solution containing about 94.1 to about 94.5 wt % of the hydrocarbon solvent has resulted in formation of products having much lower productivities. On the other hand when operating at lower temperatures, the reaction solution before prepolymerization can be more concentrated, if desired. Thus if conducting the prepolymerization at about 15xc2x0 C., the reaction solution before prepolymerization will typically be composed of about 93 to about 99 wt %, preferably about 93.5 to about 96 wt %, and more preferably about 94 to about 96 wt %, of the hydrocarbon solvent with the balance to 100% being the MAO and metallocene. In other words, in this case the solids content (MAO and metallocene, whether fed individually or as a preformed mixture) is typically in the range of from about 1 to about 7 wt %, preferably about 4 to about 6.5 wt %, and more preferably about 4 to about 6 wt %. Because lower prepolymerization temperatures tend to enable formation of products of this invention from more concentrated prepolymerization solutions, it is desirable to conduct the prepolymerization reactionsxe2x80x94at least when using MAO, the above listed-preferred metallocenes (e.g., 1-(9-fluorenyl)-1-(cyclopentadienyl)-1-(but-3-enyl)-1-(methyl) methane zirconium dichloride, etc.) and ethylenexe2x80x94at temperatures below room temperature (i.e., below about 20xc2x0 C.), and more preferably at temperatures of about 15xc2x0 C. or below, e.g., in the range of about -15xc2x0 C. to about 15xc2x0 C. Even lower temperatures can be used as long as the reaction mixture remains in the liquid state at the temperature selected.
After the prepolymerization, the resulting solid prepolymerized catalyst is separated from the liquid of the reaction mixture. Various techniques known in the art can be used for carrying out this step. For example, the material could be separated by filtration, decantation, or by vacuum evaporation. It is currently preferred, however, not to rely upon vacuum evaporation since it is considered desirable to remove substantially all of the soluble components in the liquid reaction product of the prepolymerization from the resulting solid prepolymerized catalyst before it is stored or used for subsequent polymerization. After separating the solid from the liquid the resulting solid is preferably washed with a hydrocarbon and then dried using high vacuum to remove substantially all the liquids and other volatile components that might still be associated with the solid.
From the standpoint of particle size characteristics, self-supported catalyst compositions of this invention have one or more of the following features wherein all percentages are volume percentages:
1) An average (mean) particle size in the range of about 20 to about 60 microns, desirably in the range of about 22 to about 55 microns.
2) A mean: median particle size ratio in the range of 0.7:1 to about 1.5:1, more desirably in the range of about 0.8:1 to about 1.3:1, and still more desirably in the range of about 0.9:1 to about 1.1:1.
3) A particle size distribution in which 75% of the catalyst has a particle size below 70 microns and 25% of the catalyst has a particle size of 70 microns or above, in which 50% of the catalyst has a particle size below 62 microns and 50% of the catalyst has a particle size of 62 microns or above, in which 25% of the catalyst has a particle size below 45 microns and 75% of the catalyst has a particle size of 45 microns or above, and in which no more than 5%, and desirably no more than about 2%, of the catalyst has a particle size above 400 microns.
4) A particle size distribution as described in 3) above except that no more than about 3% and more desirably no more than about 1% of the catalyst has a particle size above 300 microns.
5) A particle size distribution in which 90% of the catalyst has a particle size below 80 microns and 10% of the catalyst has a particle size of 80 microns or above, in which 75% of the catalyst has a particle size below 70 microns and 25% of the catalyst has a particle size of 70 microns or above, in which 50% of the catalyst has a particle size below 62 microns and 50% of the catalyst has a particle size of 62 microns or above, in which 25% of the catalyst has a particle size below 45 microns and 75% of the catalyst has a particle size of 45 microns or above, and in which 10% of the catalyst has a particle size below 25 microns and 90% of the catalyst has a particle size of 25 microns or above.
6) A particle size distribution as described in 5) in which no more than 5%, and desirably no more than about 2%, of the catalyst has a particle size above 400 microns.
7) A particle size distribution as described in 5) in which no more than about 3%, and more desirably no more than about 1%, of the catalyst has a particle size above 300 microns, and more desirably no more than about 1% of the catalyst has a particle size above about 250 microns.
8) A particle size distribution in which 90% of the catalyst has a particle size below 80 microns and 10% of the catalyst has a particle size of 80 microns or above, in which 75% of the catalyst has a particle size below 70 microns and 25% of the catalyst has a particle size of 70 microns or above, in which 50% of the catalyst has a particle size below 62 microns and 50% of the catalyst has a particle size of 62 microns or above, in which 25% of the catalyst has a particle size below 45 microns and 75% of the catalyst has a particle size of 45 microns or above, and in which 10% of the catalyst has a particle size below 6 microns and 90% of the catalyst has a particle size of 6 microns or above.
9) A particle size distribution as described in 8) in which no more than 5%, and desirably no more than about 2%, of the catalyst has a particle size above 400 microns.
10) A particle size distribution as described in 8) in which no more than about 3%, and more desirably no more than about 1%, of the catalyst has a particle size above 300 microns, and more desirably no more than about 1 of the catalyst has a particle size above about 250 microns.
11) The combination of 1) above and 2) above.
12) Each one of the eight (8) individual combinations composed of 1) above and one of each individual member of 3) through 10) above.
13) Each one of the eight (8) individual combinations composed of 2) above and one of each individual member of 3) through 10) above.
14) Each one of the eight (8) individual combinations composed of 1) above, 2) above and one of each individual member of 3) through 10) above.
From the standpoint of productivity determined as described elsewhere herein, self-supported catalyst compositions of this invention have one or more of the following features:
15) A productivity of at least 12,000 grams of polyethylene per gram of catalyst composition.
16) A productivity of at least 15,000 grams of polyethylene per gram of catalyst composition.
17) A productivity of at least 18,000 grams of polyethylene per gram of catalyst composition.
18) A productivity of at least 25,000 grams of polyethylene per gram of catalyst composition.
19) A productivity of at least 30,000 grams of polyethylene per gram of catalyst composition
From the combined standpoints of (i) particle size characteristics, and (ii) productivity determined as described elsewhere herein, self-supported catalyst compositions of this invention include embodiments composed of:
20) The combination of 1) above and 15) above.
21) The combination of 1) above and 16) above.
22) The combination of 1) above and 17) above.
23) The combination of 1) above and 18) above.
24) The combination of 1) above and 19) above.
25) The combination of 2) above and 15) above.
26) The combination of 2) above and 16) above.
27) The combination of 2) above and 17) above.
28) The combination of 2) above and 18) above.
29) The combination of 2) above and 19) above.
30) The combination of 11) above and 15) above.
31) The combination of 1) above and 16) above.
32) The combination of 1) above and 17) above.
33) The combination of 1) above and 18) above.
34) The combination of 1) above and 19) above.
35) The combination of 12) above and 15) above.
36) The combination of 12) above and 16) above.
37) The combination of 12) above and 17) above.
38) The combination of 12) above and 18) above.
39) The combination of 12) above and 19) above.
40) The combination of 13) above and 15) above.
41) The combination of 13) above and 16) above.
42) The combination of 13) above and 17) above.
43) The combination of 13) above and 18) above.
44) The combination of 13) above and 19) above.
45) The combination of 14) above and 15) above.
46) The combination of 14) above and 16) above.
47) The combination of 14) above and 17) above.
48) The combination of 14) above and 18) above.
49) The combination of 14) above and 19) above.
From the standpoint of ingredients from which the self-supported catalyst compositions are formed, the following are among preferred embodiments:
50) In each of 1) through 49) above, the metallocene is preferably a zirconocene, more preferably a zirconocene having only one atom of zirconium in the molecule, and still more preferably a zirconocene having two cyclopentadienyl moiety-containing groups in the molecule connected together by a bridging group.
51) In each of 1) through 49) above, the aluminoxane is preferably an alkylaluminoxane, and more preferably a methylaluminoxane.
52) In each of 1) through 49) above, the vinylolefin used in the prepolymerization is desirably a polymerizable gaseous 1-olefinic hydrocarbon, more desirably ethylene and/or propylene, and most preferably ethylene.
53) A combination of each respective metallocene of 50) with each respective aluminoxane of 51).
54) A combination of each respective metallocene of 50) with each respective vinylolefin of 52).
55) A combination of each respective aluminoxane of 51) with each respective vinylolefin of 52).
56) A combination of each respective metallocene of 50) with each respective aluminoxane of 51) and with each respective vinylolefin of 52).
The heterogeneous catalysts of this invention can be used in polymerizations conducted as slurry processes or as gas phase processes. By xe2x80x9cslurryxe2x80x9d is meant that the particulate catalyst is used as a slurry or dispersion in a suitable liquid reaction medium which may be composed of one or more ancillary solvents (e.g., liquid aromatic hydrocarbons, etc.) or an excess amount of liquid monomer to be polymerized in bulk. Generally speaking, the polymerizations are conducted at one or more temperatures in the range of about 0 to about 160xc2x0 C., and under atmospheric, subatmospheric, or superatmospheric conditions. Conventional polymerization adjuvants, such as hydrogen, may be employed if desired. Preferably polymerizations conducted in a liquid reaction medium containing a slurry or dispersion of a catalyst of this invention are conducted at temperatures in the range of about 40 to about 110xc2x0 C. Typical liquid diluents for such processes include hexane, toluene, and like materials. Typically, when conducting gas phase polymerizations, superatmospheric pressures are used, and the reactions are conducted at temperatures in the range of about 50 to about 120xc2x0 C. These gas phase polymerizations can be performed in a stirred or fluidized bed of catalyst in a pressure vessel adapted to permit the separation of product particles from unreacted gases. Thermostated ethylene, comonomer, hydrogen and an inert diluent gas such as nitrogen can be introduced or recirculated to maintain the particles at the desired polymerization reaction temperature. An aluminum alkyl such as triethylaluminum may be added as a scavenger of water, oxygen and other impurities. In such cases the aluminum alkyl is preferably employed as a solution in a suitable dry liquid hydrocarbon solvent such as toluene or xylene. Concentrations of such solutions in the range of about 5xc3x9710xe2x88x923 molar are conveniently used. But solutions of greater or lesser concentrations can be used, if desired.
Polymer product can be withdrawn continuously or semi-continuously at a rate that maintains a constant product inventory in the reactor.
Polymers can be produced pursuant to this invention by homopolymerization of polymerizable olefins, typically 1-olefins (also known as xcex1-olefins) such as ethylene, propylene, 1-butene, styrene, or copolymerization of two or more copolymerizable monomers, at least one of which is typically a 1-olefin. The other monomer(s) used in forming such copolymers can be one or more different 1-olefins and/or a diolefin, and/or a polymerizable acetylenic monomer. Normally, the hydrocarbon monomers used, such as 1-olefins, diolefins and/or acetylene monomers, will contain up to about 10 carbon atoms per molecule. Preferred 1-olefin monomers for use in the process include ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. It is particularly preferred to use the particulate catalysts of this invention in the polymerization of ethylene, or propylene, or ethylene and at least one C3-C8 1-olefin copolymerizable with ethylene. Typical diolefin monomers include 1,6-which can be used to form terpolymers with ethylene and propylene include hexadiene, norbornadiene, and similar copolymerizable diene hydrocarbons. 1-Heptyne and 1-octyne are illustrative of suitable acetylenic monomers which can be used.
Because of the higher activity and productivity of the catalysts of this invention, the amount of the present heterogeneous catalysts used in olefin polymerizations can be somewhat less than is typically used in olefin polymerizations conducted on an equivalent scale. For example, in conducting homopolymerization of ethylene in a 2-liter autoclave with a constant ethylene pressure of 450 psig, excellent results have been achieved using as little as 5 milligrams of catalyst per batch polymerization reaction. Thus in general the polymerizations and copolymerizations conducted pursuant to this invention are carried out using a catalytically effective amount of the heterogeneous catalyst, which amount may be varied depending upon such factors such as the type of polymerization being conducted, the polymerization conditions being used, and the type of reaction equipment in which the polymerization is being conducted. In many cases, the amount of the catalyst of this invention used will be such as to provide in the range of about 0.000001 to about 0.01 percent by weight of Group 4 metal based on the weight of the monomer(s) being polymerized.
After polymerization and deactivation of the catalyst in a conventional manner, the product polymer can be recovered from the polymerization reactor by any suitable means. When conducting the process with a slurry or dispersion of the catalyst in a liquid medium the product typically is recovered by a physical separation technique (e.g. decantation, etc.). The recovered polymer is usually washed with one or more suitably volatile solvents to remove residual polymerization solvent or other impurities, and then dried, typically under reduced pressure with or without addition of heat. When conducting the process as a gas phase polymerization, the product after removal from the gas phase reactor is typically freed of residual monomer by means of a nitrogen purge, and often can be used without further catalyst deactivation or catalyst removal.
When preparing polymers pursuant to this invention conditions may be used for preparing unimodal or multimodal polymer types. For example, mixtures of catalysts of this invention formed from two or more different metallocenes having different propagation and termination rate constants for ethylene polymerizations can be used in preparing polymers having broad molecular weight distributions of the multimodal type.
To determine productivity of catalyst particles the following polymerization procedure should be used: A two-liter autoclave is used to carry the polymerizations. The reactor is rinsed with 1100 grams of toluene at a temperature of at least 140xc2x0 C. for at least 10 minutes. The reactor is then purged with low pressure nitrogen for 5 minutes and then evacuated under vacuum for at least one hour at  greater than 140xc2x0 C. The reactor is purged and vented twice with 600 psig nitrogen and twice with one liter (about 80 psig) of isobutane. The isobutane is vented off, but a small isobutane purge on the reactor is maintained. Once the reactor has cooled to below 40xc2x0 C., about 15 mg of the particulate metallocene/aluminoxane catalyst as a slurry in 2.0 mL of hexane/TEA solution is charged to the reactor against the counterflow of isobutane. The reactor is then filled with 1.0 liter of isobutane. The agitator is set to 1100 rpm and the reactor is heated to 91.5xc2x0 C. With the reactor temperature at 91.5xc2x0 C., ethylene is charged in to give a reactor pressure of 450 psig. Ethylene is polymerized for 1.0 hour. After 1.0 hour, the reactor is slowly vented and cooled. Polyethylene (PE) is removed and weighed. Productivity is calculated by using the expression:
grams PE/grams catalystxc3x97hour.
Productivity is thus determined in the above procedure using the catalyst composition in the form of solid particles, the catalyst is not in solution.
It will be understood and appreciated that the productivity as determined by the above procedure is a property or characteristic of the particulate catalyst to be determined when the catalyst is fresh, the term xe2x80x9cfreshxe2x80x9d being used in the sense that the catalyst has not been previously used in a polymerization reaction. It is, of course, not necessary to test every batch of fresh catalyst for its productivity, provided the materials and conditions used for preparing the catalyst remain the same from batch to batch, and as long as there is no reason to question the productivity of any particular batch of fresh catalyst where the productivity of one or more prior batches had previously been found to be in accordance with this invention. Thus productivity is a property or inherent characteristic of the particulate catalysts of this invention which manifests itself when and if one or more samples of fresh particulate catalyst are tested for productivity.
It will also be understood and appreciated that the specific surface area is another characteristic of the fresh catalyst.
To determine specific surface area of the particulate catalysts of this invention the well-known BET technique is used. The BET technique (named after the inventors, Braunauer, Emmnett, and Teller) consists of (1) removing adsorbed gases from the sample with heat and vacuum, (2) adsorbing a mono-layer of nitrogen on the surface at liquid nitrogen temperature, (3) measuring the amount of adsorbed nitrogen, and (4) calculating the total surface area of the sample from an assumed cross-sectional area of nitrogen molecules. The total surface area is divided by the sample weight to yield the specific surface area. Specific surface area is defined as the exposed surface area of 1 gram of the sample tested. For best results, the Coulter(copyright) LS-230 laser diffraction spectrometer, or equivalent instrument, if any, should be used.